EP0307717A2 - Process for preparing phosphanes - Google Patents
Process for preparing phosphanes Download PDFInfo
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- EP0307717A2 EP0307717A2 EP88114170A EP88114170A EP0307717A2 EP 0307717 A2 EP0307717 A2 EP 0307717A2 EP 88114170 A EP88114170 A EP 88114170A EP 88114170 A EP88114170 A EP 88114170A EP 0307717 A2 EP0307717 A2 EP 0307717A2
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- European Patent Office
- Prior art keywords
- reaction
- bar
- phosphines
- alkali hydroxide
- temperatures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000004519 manufacturing process Methods 0.000 title description 3
- 229910000064 phosphane Inorganic materials 0.000 title 1
- 150000003002 phosphanes Chemical class 0.000 title 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003003 phosphines Chemical class 0.000 claims abstract description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 10
- 229960001760 dimethyl sulfoxide Drugs 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- LRMLWYXJORUTBG-UHFFFAOYSA-N dimethylphosphorylmethane Chemical compound CP(C)(C)=O LRMLWYXJORUTBG-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical class C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H
Definitions
- the present invention relates to the production of phosphines of the general formulas R n PH 3-n (I) H2P- (CH2) m -PH2 (II) or (C6H5) 2P-CH2-PH2 (III) in which R represents a straight-chain or branched alkyl group having 1 to 24 carbon atoms or a cycloalkyl, benzyl or allyl group, m corresponds to 2, 3 or 4 and n is 1 or 2.
- Alkylphosphines are becoming increasingly important as building blocks for the production of higher organophosphorus compounds. So far, there has been no lack of attempts to obtain these phosphines, with very different approaches being followed.
- phosphines of the general formulas I to III mentioned at the beginning are obtained from readily accessible hydrogen phosphide (PH3) as the starting product if hydrogen phosphide is present in the presence of both a 50 to 70% strength by weight aqueous alkali hydroxide solution and of dimethyl sulfoxide with reagents of the general formula RX, X (CH2) m X (C6H5) 2P-CH2-X, in which R and m have the meanings given and X is chlorine or bromine, at temperatures between 0 and 70 ° C and a pressure from 0 to 10 bar, using at least 1 mol of alkali hydroxide per mol of X.
- reaction is carried out at temperatures from 0 to 50 ° C. and at overpressures between 0.1 and 8 bar.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Description
Vorliegende Erfindung betrifft die Herstellung von Phosphanen der allgemeinen Formeln
RnPH3-n (I)
H₂P-(CH₂)m-PH₂ (II) oder
(C₆H₅)₂P-CH₂-PH₂ (III)
in denen R eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 24 C-Atomen oder eine Cycloalkyl-, Benzyl- oder Allylgruppe darstellt, m 2, 3 oder 4 entspricht und n gleich 1 oder 2 ist.The present invention relates to the production of phosphines of the general formulas
R n PH 3-n (I)
H₂P- (CH₂) m -PH₂ (II) or
(C₆H₅) ₂P-CH₂-PH₂ (III)
in which R represents a straight-chain or branched alkyl group having 1 to 24 carbon atoms or a cycloalkyl, benzyl or allyl group, m corresponds to 2, 3 or 4 and n is 1 or 2.
Alkylphosphane erhalten zunehmend technische Bedeutung als Bausteine zur Herstellung höherer phosphororganischer Verbindungen. Es hat daher bislang nicht an Versuchen gefehlt, diese Phosphane zu gewinnen, wobei sehr unterschiedliche Wege beschritten wurden.Alkylphosphines are becoming increasingly important as building blocks for the production of higher organophosphorus compounds. So far, there has been no lack of attempts to obtain these phosphines, with very different approaches being followed.
So ist u.a. auch betreits die Umsetzung von Phosphan (PH₃) mit Methyljodid in Gegenwart von KOH und Dimethylsulfoxid (DMSO) beschrieben worden (William L. Jolly, Inorganic Synthesis, Vol. 11 (1968) Seiten 124 und 126).Among other things, also the reaction of phosphine (PH₃) with methyl iodide in the presence of KOH and dimethyl sulfoxide (DMSO) has been described (William L. Jolly, Inorganic Synthesis, Vol. 11 (1968) pages 124 and 126).
Nachteilig an dieser Arbeitsweise ist jedoch, daß sie nur für Arbeiten im Labormaßstab in kleinen Mengen geeignet ist und das eingesetzte Methyljodid sehr teuer, giftig und krebserregend ist. Außerdem ist es erforderlich, KOH in feingemahlener fester Form, suspendiert in DMSO, einzusetzen.The disadvantage of this method of operation is, however, that it is only suitable for work on a laboratory scale in small quantities and that the methyl iodide used is very expensive, toxic and carcinogenic. It is also necessary to use KOH in finely ground solid form, suspended in DMSO.
Bekannt ist auch, Phenyl- und Diphenylphosphane in Gegenwart von Dimethylsulfoxid (DMSO) und wäßriger konzentrierter KOH mit Hilfe von Alkylhalogeniden zu den entsprechenden sekundären und tertiären Phosphanen umzusetzen (Synthesis 1986, Seiten 8 bis 22).It is also known to convert phenyl- and diphenylphosphines in the presence of dimethyl sulfoxide (DMSO) and aqueous concentrated KOH with the aid of alkyl halides to the corresponding secondary and tertiary phosphines (Synthesis 1986, pages 8 to 22).
Ein Nachteil dieses Verfahrens ist, daß dieser Weg nur zu sekundären und tertiären Phosphanen führt, die zwangsläufig zumindest eine Phenylgruppe als Substituent tragen.A disadvantage of this process is that this route only leads to secondary and tertiary phosphines which inevitably carry at least one phenyl group as a substituent.
Überraschenderweise wurde nun gefunden, daß man Phosphane der eingangs angeführten allgemeinen Formeln I bis III aus leicht zugänglichem Phosphorwasserstoff (PH₃) als Ausgangsprodukt erhält, wenn man Phosphorwasserstoff in Gegenwart sowohl einer 50 bis 70 gew%igen wäßrigen Alkali-Hydroxid-Lösung als auch von Dimethylsulfoxid mit Reagenzien der allgemeinen Formel RX, X(CH₂)mX (C₆H₅)₂P-CH₂-X, in denen R und m die angegebenen Bedeutungen haben und X für Chlor oder Brom steht, bei Temperaturen zwischen 0 und 70°C und einem Überdruck von 0 bis 10 bar umsetzt, wobei man pro Mol X jeweils mindestens 1 Mol Alkali-Hydroxid einsetzt.Surprisingly, it has now been found that phosphines of the general formulas I to III mentioned at the beginning are obtained from readily accessible hydrogen phosphide (PH₃) as the starting product if hydrogen phosphide is present in the presence of both a 50 to 70% strength by weight aqueous alkali hydroxide solution and of dimethyl sulfoxide with reagents of the general formula RX, X (CH₂) m X (C₆H₅) ₂P-CH₂-X, in which R and m have the meanings given and X is chlorine or bromine, at temperatures between 0 and 70 ° C and a pressure from 0 to 10 bar, using at least 1 mol of alkali hydroxide per mol of X.
Vorteilhafte Ausgestaltungen dieses Verfahrens sind z.B., daß die Umsetzung bei Temperaturen von 0 bis 50°C und bei Überdrucken zwischen 0,1 und 8 bar durchgeführt wird.Advantageous embodiments of this process are, for example, that the reaction is carried out at temperatures from 0 to 50 ° C. and at overpressures between 0.1 and 8 bar.
In den nachfolgenden Tabellen sind als Beispiele Produkte aufgeführt, die durch Umsetzung von Phosphorwasserstoff mit verschiedenen Reagenzien erhalten wurden.In the tables below, examples are given of products obtained by reacting hydrogen phosphide with various reagents.
Für die Umsetzung der bei Normalbedingungen flüssigen Halogenverbindungen kann das folgende einfache Verfahren verwendet werden (Methode A, Beispiele 1 bis 6):The following simple method can be used to convert the halogen compounds which are liquid under normal conditions (Method A, Examples 1 to 6):
In einer Rührapparatur (3-Halskolben, versehen mit Rührer, Tropftrichter, Rückflußkühler) suspendierte man unter starkem Rühren 56 %ige wäßrige KOH-Lösung in DMSO. Durch Spülen mit Stickstoff befreite man das Reaktionssystem von Sauerstoff. Danach wurde PH₃ mit einem Überdruck von ca. 100 mbar bis zur Sättigung eingeleitet. In diese Lösung wurde das jeweilige Reagenz getropft. Das Einsetzen der Reaktion konnte leicht an der raschen Absorption erkannt werden, durch Nachdosieren wurde der PH₃-Überdruck konstant gehalten. Nebenreaktionen des PH₃ wurden nicht beobachtet. Nach Beendigung der Reaktion wurde der Ansatz bei 0°C (1 : 1) mit entgastem Wasser versetzt, wobei Phasentrennung eintrat. Zur besseren Abtrennung der entstandenen Phosphane wurde mit n-Pentan extrahiert. Der Extrakt wurde mit Wasser gewaschen und über Natriumsulfat getrocknet. Das Lösungsmittel wurde bei Normaldruck abdestilliert und der Rückstand fraktioniert.
Die physikalischen Daten der erhaltenen Reaktionsprodukte entsprachen in allen Fällen den aus der Literatur für diese Verbindungen bekannten Werten.56% strength aqueous KOH solution in DMSO was suspended in a stirring apparatus (3-neck flask equipped with a stirrer, dropping funnel, reflux condenser) with vigorous stirring. The reaction system was freed of oxygen by flushing with nitrogen. Then PH₃ was initiated with an overpressure of about 100 mbar until saturation. The respective reagent was dropped into this solution. The onset of the reaction could be easily recognized by the rapid absorption, the PH₃ overpressure was kept constant by metering. Side reactions of the PH₃ were not observed. After the reaction had ended, degassed water was added to the batch at 0 ° C. (1: 1), phase separation occurring. For better separation of the resulting phosphines, extraction was carried out with n-pentane. The extract was washed with water and dried over sodium sulfate. The solvent was distilled off at normal pressure and the residue was fractionated.
In all cases, the physical data of the reaction products obtained corresponded to the values known from the literature for these compounds.
Die Umsetzung von bei Normaltemperatur- und -druck gasförmigen Alkylhalogeniden wird vorteilhafterweise nach Methode B durchgeführt:The reaction of gaseous alkyl halides at normal temperature and pressure is advantageously carried out according to method B:
In einem 5-l-Laborautoklaven wurden nacheinander bei ca. -40°C die gewünschten Mengen Alkylhalogenid und PH₃ einkondensiert. Nach Erwärmen auf Kühlwassertemperatur pumpte man zunächst 500 ml DMSO und danach eine Lösung von 450 g KOH in 250 ml H₂O (ca. 500 ml) hinzu. Mit dem Zudosieren der KOH-Lösung setzte die exotherme Reaktion ein, wobei die Reaktionstemperatur durch Mantelkühlung auf die angegebenen Maximalwerte begrenzt wurde. Der Druck sank während der Dosierzeit der KOH-Lösung (30 Min.) deutlich ab.In a 5-liter laboratory autoclave, the desired amounts of alkyl halide and PH₃ were condensed in at about -40 ° C. After heating to cooling water temperature, 500 ml of DMSO and then a solution of 450 g of KOH in 250 ml of H₂O (about 500 ml) were pumped in. With the addition of the KOH solution, the exothermic reaction started, the reaction temperature being limited to the specified maximum values by jacket cooling. The pressure dropped significantly during the metering time of the KOH solution (30 min.).
Nach Beendigung der Reaktion entspannte man die Gasphase über 3 mit je 250 g Konz. HCl gefüllte Waschflaschen, wobei der Reaktor auf maximal 50°C erwärmt wurde. Methylphosphan (Kp:-17°C) sowie ein Teil des gebildeten Ethylphosphans (Kp:25°C) bzw. Dimethylphosphans (Kp:21°C) wurden dabei quantitativ in Form ihrer HCl-Addukte abgefangen. Nicht absorbierte Restgase (Spülstickstoff, evt. nicht umgesetztes PH₃ sowie Methyl- bzw. Ethylchlorid) wurden in einer nachgeschalteten Brennkammer verbrannt. Für die quantitative Analyse der gebildeten Produkte wurden P-Elementaranalysen der HCl- und der DMSO-Lösung in Verbindung mit ³¹ P-NMR-Spektroskopie herangezogen.After the reaction had ended, the gas phase was let down over 3 wash bottles filled with 250 g conc. HCl each, the reactor being heated to a maximum of 50.degree. Methylphosphine (bp: -17 ° C) and part of the ethylphosphane (bp: 25 ° C) or dimethylphosphane (bp: 21 ° C) were quantitatively captured in the form of their HCl adducts. Residual gases not absorbed (nitrogen purge, possibly unreacted PH₃ and methyl or ethyl chloride) were burned in a downstream combustion chamber. For the quantitative analysis of the products formed, P elementary analyzes of the HCl and DMSO solutions in conjunction with 31 P NMR spectroscopy were used.
In den wässrigen Phasen konnte kein Phosphor nachgewiesen werden (< 0,1 %).No phosphorus could be detected in the aqueous phases (<0.1%).
Wie die nachfolgende Tabelle 2 zeigt, ist das Arbeiten in wässriger Alkalihyroxid-Lösung in überraschender Weise von Vorteil. Gemäß Vergleichsbeispiel 9 wird bei Einsatz von festem Alklihydroxid eine deutlich schlechtere Umsetzung des PH₃ beobachtet. Ein weiterer Nachteil ist ferner der hohe Anteil an unerwünschtem Trimethylphosphanoxid in der DMSO-Phase. Möglicherweise wird unter den in Beispiel 9 beschriebenen Reaktionsbedingungen auch Trimethylphosphan (Kp:40°C) in erheblichem Umfang gebildet, das durch DMSO schnell zum entsprechenden Phosphanoxid oxidiert wird.
Claims (3)
RnPH3-n (I)
H₂P-(CH₂)m-PH₂ (II) oder
(C₆H₅)₂P-CH₂-PH₂ (III)
in denen R eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 24 C-Atomen oder eine Cycloalkyl-, Benzyl-, oder Allylgruppe darstellt, m 2, 3 oder 4 entspricht und n gleich 1 oder 2 ist, dadurch gekennzeichnet, daß man Phosphorwasserstoff in Gewenwart sowohl einer 50 bis 70 gew%igen, wäßrigen Alkali-Hydroxid-Lösung als auch von Dimethylsulfoxid mit Reagenzien der allgemeinen Formeln RX, X(CH₂)mX oder (C₆H₅)₂P-CH₂-X, in denen R und m die angegebenen Bedeutungen haben und X für Chlor oder Brom steht, bei Temperaturen zwischen 0 und 70°C und einen Überdruck von 0 bis 10 bar umsetzt, wobei man pro Mol X jeweils mindestens 1 Mol Alkali-Hydroxid einsetzt.1. Process for the preparation of phosphines of the general formulas
R n PH 3-n (I)
H₂P- (CH₂) m -PH₂ (II) or
(C₆H₅) ₂P-CH₂-PH₂ (III)
in which R represents a straight-chain or branched alkyl group having 1 to 24 carbon atoms or a cycloalkyl, benzyl or allyl group, m corresponds to 2, 3 or 4 and n is 1 or 2, characterized in that hydrogen phosphide in Gewenwart both a 50 to 70% by weight aqueous alkali hydroxide solution and dimethyl sulfoxide with reagents of the general formulas RX, X (CH₂) m X or (C₆H₅) ₂P-CH₂-X, in which R and m have the meanings given have and X represents chlorine or bromine, at temperatures between 0 and 70 ° C and an excess pressure of 0 to 10 bar, wherein at least 1 mole of alkali hydroxide is used per mole of X.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873731425 DE3731425A1 (en) | 1987-09-18 | 1987-09-18 | METHOD FOR PRODUCING PHOSPHANS |
| DE3731425 | 1987-09-18 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0307717A2 true EP0307717A2 (en) | 1989-03-22 |
| EP0307717A3 EP0307717A3 (en) | 1990-07-18 |
| EP0307717B1 EP0307717B1 (en) | 1992-10-07 |
Family
ID=6336328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88114170A Expired - Lifetime EP0307717B1 (en) | 1987-09-18 | 1988-08-31 | Process for preparing phosphanes |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0307717B1 (en) |
| JP (1) | JPH01102091A (en) |
| DD (1) | DD273636A5 (en) |
| DE (2) | DE3731425A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0638578A1 (en) * | 1993-07-31 | 1995-02-15 | Hoechst Aktiengesellschaft | Secondary and primary phosphanes and process for their preparation |
| EP3666782A1 (en) * | 2018-12-11 | 2020-06-17 | Umicore Ag & Co. Kg | Lithium alkyl aluminates, use of a lithium alkyl aluminate as a transfer reagent, method for transferring at least one remainder r, e(x)q-prp compounds and their use, substrate and method for producing lithium alkyl aluminates |
-
1987
- 1987-09-18 DE DE19873731425 patent/DE3731425A1/en not_active Withdrawn
-
1988
- 1988-08-31 EP EP88114170A patent/EP0307717B1/en not_active Expired - Lifetime
- 1988-08-31 DE DE8888114170T patent/DE3875213D1/en not_active Expired - Fee Related
- 1988-09-16 DD DD88319867A patent/DD273636A5/en not_active IP Right Cessation
- 1988-09-19 JP JP63232755A patent/JPH01102091A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| HOUBEN-WEYL, Methoden der Organischen Chemie, Band XII/1, 1963, Seite 17, herausgegeben von E. MULLER, Georg Thieme Verlag, Stuttgart, DE * |
| JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY, Nr. 3, M{rz 1986, Seiten 198-208; E.N. TSVETKOV et al.: "A simple synthesis and some synthetic applications of substituted phosphide and phosphinite anions" * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0638578A1 (en) * | 1993-07-31 | 1995-02-15 | Hoechst Aktiengesellschaft | Secondary and primary phosphanes and process for their preparation |
| US5925785A (en) * | 1993-07-31 | 1999-07-20 | Celanese Gmbh | Secondary and tertiary phosphines and processes for their preparation |
| EP3666782A1 (en) * | 2018-12-11 | 2020-06-17 | Umicore Ag & Co. Kg | Lithium alkyl aluminates, use of a lithium alkyl aluminate as a transfer reagent, method for transferring at least one remainder r, e(x)q-prp compounds and their use, substrate and method for producing lithium alkyl aluminates |
| WO2020120148A1 (en) * | 2018-12-11 | 2020-06-18 | Umicore Ag. & Co. Kg. | Lithium alkyl aluminates as alkyl transfer reagents |
| US11384102B2 (en) | 2018-12-11 | 2022-07-12 | Umicore Ag & Co. Kg | Lithium alkyl aluminates as alkyl transfer reagents |
Also Published As
| Publication number | Publication date |
|---|---|
| DD273636A5 (en) | 1989-11-22 |
| EP0307717A3 (en) | 1990-07-18 |
| JPH01102091A (en) | 1989-04-19 |
| EP0307717B1 (en) | 1992-10-07 |
| DE3731425A1 (en) | 1989-04-06 |
| DE3875213D1 (en) | 1992-11-12 |
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